Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23K—FODDER
  • A23K20/00—Accessory food factors for animal feeding-stuffs
  • A23K20/10—Organic substances
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
  • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
  • A23L33/16—Inorganic salts, minerals or trace elements
  • A23L33/165—Complexes or chelates
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05B—PHOSPHATIC FERTILISERS
  • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon

Definitions

• the present invention is concerned with novel mineral-containing polymeric compositions of matter which are highly useful as enrichments for foods and the like. More particularly, it is concerned with such compositions and methods of synthesis thereof, wherein the compositions exhibit very high dispersibility in aqueous media, thereby rendering the compositions useful as fortificants in a wide variety of food products.
• the food industry has long sought stable water-dispersible forms of calcium, magnesium, phosphorus, potassium, iron and other trace elements in order that significant amounts of these essential nutrients can be introduced into food systems without adding attendant superfluous bulk.
• the mineral-containing substances must be essentially odorless, colorless, tasteless, and be produceable at modest cost.
• such products must exhibit stability when subjected to the condition extremes dictated by formulation, processing and storage.
• fabricated foods have been rapidly increasing in number, and their peak appeal has likewise increased because of enhanced organoleptic properties, convenience, and economic and nutritional values.
• fabricated (non-dairy) foods exemplified by margarine, imitation ice cream, non-dairy creamers, whipped topping mixes and prewhipped toppings have made a major impact on sales of counterpart traditional foods and beverages.
• non-dairy milks which may be completely free of milk protein.
• a major problem confronting the fabricated food industry is in designing or formulating products which are essentially equal to their natural counterparts on a nutritional basis, particularly with respect to mineral content.
• non-dairy milks it has heretofore been impossible to provide the desired amounts of calcium, inasmuch as there has been no relatively inexpensive and readily available calcium-containing composition which will remain in aqueous dispersion.
• solubility or dispersibility in aqueous media is also present to a greater or lesser degree with respect to other vital nutrients such as magnesium, iron, copper, boron, zinc, manganese and molybdenum, and therefore use of these nutrients has been limited in fabricated foods.
• compositions of matter which are generally of polymeric or quasi-polymeric form and it is theorized that they have high molecular weights of at least about 300,000.
• the compositions contain polyvalent cations taken from the group consisting of calcium, magnesium, iron, copper, boron, manganese, molybdenum, nickel, and zinc, and surprisingly exhibit high degrees of dispersibility or solubility in aqueous media.
• the compositions also include an organic acid moiety having at least three carboxyl groups therein, such as a citrate moiety; and in some instances adjuncts such as malto-dextrins and corn syrup, ranging in D.E.
• sucrose, dextrose, galactose, arabinose, ribose, xylose, maltose, lactose, raffinose, fructose, polyalcohols, i.e., glycerin or propylene glycol can be associated with the overall compositions to give an increase in dispersibility.
• a method of synthesis of the mineral-containing compositions is also in the ambit of the invention, and broadly comprises the steps of admixing, in water, a cation source, an alkali metal phosphate source, and an organic acid having at least three carboxyl groups therein.
• the molar ratio of the alkali metal ions to phosphate ions is within the range of from about 1:1 to 6:1.
• the final step in the process involves heating the admixture for a sufficient period of time and at a temperature to yield water-dispersible products. Such products can be stored for relatively long periods of time at varying temperature conditions while nevertheless maintaining the desirable dispersibility in water or other aqueous media.
• Mineral-containing compositions in accordance with the present invention include a moiety of the generalized formula ##STR2## wherein M 1 and M 2 are respectively taken from the group consisting of calcium, manganese, iron, copper, boron, manganese, molybdenum, nickel, and zinc, A 1 and A 2 are respectively taken from the group consisting of hydrogen and the alkali metals, and X is an organic acid moiety having at least three carboxyl groups therein.
• a 1 and A 2 are respectively taken from the group consisting of hydrogen, lithium, potassium and sodium, and said acid moiety is a citrate moiety of the formula ##STR3## so that the overall moiety, in the most preferred form, has the following generalized formula: ##STR4##
• compositions of matter are in the form of polymers or quasi-polymers having a molecular weight exceeding about 300,000, with the depicted moieties, or analogs thereof, being recurrent throughout the compositions.
• compositions in accordance with the present invention exhibit surprising and very high dispersibilities in water or other aqueous media.
• the compositions of the invention should exhibit an aqueous dispersability such that at least about 30% by weight of the theoretically available, non-alkali metal cations present therein are dispersed in water at ambient temperature.
• cation-containing products of the invention having high degrees of dispersibility are made by first forming an admixture in water of respective quantities of: (1) a cation source selected from the group consisting of compounds of calcium, magnesium, iron, copper, boron, manganese, molybdenum, nickel, and zinc; (2) a potassium phosphate source selected from the group consisting of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, and a mixture of phosphoric acid and a potassium source; and (3) an organic acid having at least three carboxyl groups therein.
• a cation source selected from the group consisting of compounds of calcium, magnesium, iron, copper, boron, manganese, molybdenum, nickel, and zinc
• a potassium phosphate source selected from the group consisting of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, and a mixture of phosphoric acid and a potassium source
• an organic acid having
• the molar ratios of the starting materials should preferably be as follows: for phosphate ion to acid, from about 0.5:1 to 3:1, most preferably about 1:1; for alkali metal ions to phosphate ions, from about 1:1 to 6:1, most preferably about 2:1; for non-alkali metal cations to phosphate, from about 0.5:1 to 3:1, most preferably about 2:1; for non-alkali metal cations to acid, from about 1:1 to 5:1, most preferably about 2:1; and for alkali metal ions to acid, from about 0.5:1 to 7:1, most preferably about 2:1.
• the starting admixture should be stoichiometrically balanced to achieve the desired end composition.
• the next and final step of the method involves simply heating the admixture for a sufficient period of time and at a temperature to yield the desired products.
• this involves heating the admixture to a temperature of from about 150° to 400° F., and thereafter further admixing the admixture at this temperature for a period of from about 10 to 60 minutes.
• a preferred hydroxyl-containing adjunct such as corn syrup, glycerine, sucrose or dextrose
• this should be added cold with the initial ingredients with thorough mixing.
• the initial admixture should contain at least about 60 percent by weight water, and in many instances significantly more than this figure.
• it has been found desirable to add the respective components of the admixture by first adding the cation source to water followed by a period of mixing of from about 1 to 5 minutes; then adding the alkali metal phosphate source with mixing for a period of from about 1 to 5 minutes; and finally addition of the organic acid (preferably citric acid) with mixing for a period of from about 1 to 5 minutes.
• the described heating and further mixing step can be effected.
• aqueous product If it is desired to produce a dry, reconstitutable product, it is generally preferred to homogenize the aqueous product or subject it to high shear mixing followed by drying (e.g., spray drying).
• the resultant solid or granular product can be reconstituted in aqueous media and exhibits substantially identical dispersibility properties as compared with the original liquid.
• the products of the present invention can be stored virtually indefinitely without loss of their desirable properties, and are admirably suited as fortificants in connection with fabricated foods such as non-dairy milks and the like.
• products may have significant utility as fertigation agents.
• a water dispersible mineral enrichment composition was made using the ingredients set forth in Table I below. Each ingredient was added in the order listed in Table I to a 2 liter glass beaker, and the ingredients were stirred with a high shear "Tekmar" mixer throughout the synthesis. During the initial blending, the beaker was placed in an ice water bath to prevent extreme temperature rise. The temperature at each addition and mixing times are noted in Table I.
• the pH of the composition after initial blending was 6.75.
• the composition was then heated in a hot water bath over a hot plate while mixing was continued. This treatment was continued for approximately 35 minutes until a temperature of 180° was reached.
• the pH of the mixture at this time was 6.45.
• composition A portion of this composition was placed in a sterilized bottle.
• the composition was semitransparent and hazy white in color, and appeared homogeneous throughout.
• Another portion was placed in a bottle and heated in a pressure cooker at 250° F. (15 p.s.i. steam pressure) for 15 minutes. This preparation was yellow in color and more transparent than the former sample, although a very slight haziness was observed.
• the composition was prepared as described in Example 1. After mixing at room temperature, (maintained by ice/water bath) the pH was 6.7.
• the composition was then heated to 180° F. (over approximately 30 minutes). The pH at this time was 6.65.
• a sample taken after heating exhibited, after a few minutes at room temperature, a semitransparent upper layer, a dense cloudy layer, and a small amount of a white powdery precipitate.
• the 180° F. sample After remaining at room temperature for about five days, the 180° F. sample exhibited a white flocculent layer filling approximately the bottom 40% of the container. The single upper layer was nearly transparent.
• the 250° F. sample at this time appeared to be a nearly homogeneous translucent fluid with a very small amount of white precipitate.
• compositions described in Examples 1 and 2 are useful from a nutritional standpoint for mineral fortification of foods for general consumption such as juices, carbonated and noncarbonated beverages, dairy analogs, soups, broths and other foods in which insoluble minerals are unfeasible. Other areas of application would be in infant formulas, pet foods, animal feeds, special dietary supplements or in a mineral "tonic", and for use as a fertilizer.
• compositions are capable of being spray dried, drum dried, vacuum dried or otherwise dehydrated and are then readily soluble or dispersible in a wide variety of aqueous media. They can be designed to provide a portion or all of the RDA of calcium, magnesium, iron, copper, zinc and phosphorus while having little or no effect on the taste or physical characteristics of the product to which it is added.
• a mineral composition was prepared using the above ingredients in a 2 liter glass beaker which was placed in an ice water bath to prevent any extreme temperature rise during the initial blending. Continuous vigorous agitation was supplied with a "TEKMAR" mixer throughout the entire preparation.
• the composition was then heated in a water bath over a hot plate, while agitation was continued for approximately 35 minutes until a temperature of 180° F. was reached.
• the pH of the composition was 6.45.
• a water dispersible calcium, magnesium and phosphorus mineral enrichment composition of commercial proportions was made using the ingredients set forth in Table IV below. Each ingredient was added in the order listed in Table IV to a 200 gallon jacketed stainless steel mixing vessel equipped with a double counter-rotating stirrer and a loop circulation system whereby the product was drawn from the bottom outlet of the vessel and pumped into the top surface of the product. The temperature at each addition was controlled by a water-steam mixing valve and the times (Hold Time) following the addition of each ingredient are recorded in Table IV.
• composition was homogenized hot at 3000 p.s.i.-500 p.s.i., first and second stage respectively through a Gaulin homogenizer and then pumped to a Damrow spray drier and dried.
• the resultant dried powder in a 10% aqueous dispersion had a pH of 6.6 and a clear viscous slightly yellow solution resulted on the addition of 150 grams of the powdered composition to 100 grams of water (60% solids).
• the nutrient composition of the non-dairy milk formulation was patterned after the above.
• the Case unit includes a stainless steel, conical vessel having therein a series of superposed, perforated plates, with the perforations in respective plates being out of alignment with those of adjacent plates.
• the unit also includes a recirculation line for taking liquid from the bottom of the vessel back to the top thereof, and a positive displacement pump is interposed in the recirculation line for relatively high pressure recirculation of liquid material.
• the liquid components are recirculated through the emulsification apparatus and are subjected to vigorous agitation and shear.
• direct steam addition is provided for further agitation and heating of the liquid product during recirculation thereof.
• the starch-derived carbohydrate material and water are first admixed and run through the Case emulsifier to ensure complete dispersion thereof.
• the ingredients following were then added at the temperature stated in Table V and mixed for the period stated under Hold Time prior to the addition of the next ingredient.
• This product was immediately cooled to 38° F., and the following nutritional fortification was intimately added thereto using a high shear mixer:
• the pH of this fortified synthetic milk was measured at 6.8, and freeze-thaw stability was excellent.
• the product exhibited all of the attributes of whole milk, i.e., general appearance, color, mouth feel, correct residual mouth feel and aftertaste. Also, no precipitation of solids from the liquid was observed.
• Example 4 The spray dried product prepared in Example 4 was tested for bioavailability of calcium and phosphorus in feeding studies utilizing weanling rats.
• a standard purified diet for rats was used.
• the control diet contained CaCO 3 and NaH 2 PO 4 as the sources of calcium and phosphorus.
• the test diet contained the product of Example 4 as the principal source of calcium, with CaCO 3 added to obtain a final calcium level of 0.60%.
• a third diet consisted of Purina Lab Chow.
• control rats did not grow as well as the rats on the test diet or those on the Purina Lab Chow.
• the bioavailability of the test product is reflected in the bone ash data expressed as a percent of the dry bone weight.
• the femur bone was utilized for the assay.
• compositions in accordance with the invention were produced, with various reactants and reactant ratios being tested.
• the composition was made as follows:
• a steam-water mixture was directed to the kettle jacket to begin heating the material therein. Mixing was continued during this step. When the temperature of the mixture reached about 200° F., a steam/water mix was employed to maintain the temperature level, and a final mixing step of about 30 minutes was conducted.
• the products were homogenized (3500 p.s.i. first stage, 500 p.s.i. second stage or alternately a single stage, 2000 p.s.i.), and thereafter spray dried to yield a powdered product which could be reconstituted in water.
• compositions in accordance with the invention should preferably exhibit an aqueous dispersibility such that at least about 30% by weight of the theoretically available, non-alkali metal cations present are dispersed in water at ambient temperature.
• aqueous dispersibility such that at least about 30% by weight of the theoretically available, non-alkali metal cations present are dispersed in water at ambient temperature.
• a mineral nutrient composition patterned after the calcium, magnesium and phosphorus composition of whole milk was prepared and spray dried using the following formulation table and the procedure described in Example 7.

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• Chemical & Material Sciences (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Food Science & Technology (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Animal Husbandry (AREA)
• Inorganic Chemistry (AREA)
• Nutrition Science (AREA)
• Mycology (AREA)
• Zoology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Coloring Foods And Improving Nutritive Qualities (AREA)
• Dairy Products (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Medicines Containing Material From Animals Or Micro-Organisms (AREA)

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• 1978
  • 1978-12-19 US US05/970,935 patent/US4214996A/en not_active Expired - Lifetime
• 1979
  • 1979-10-11 DE DE7979302179T patent/DE2966618D1/de not_active Expired
  • 1979-10-11 EP EP79302179A patent/EP0012500B1/en not_active Expired
  • 1979-10-11 AT AT79302179T patent/ATE6021T1/de not_active IP Right Cessation
  • 1979-10-18 IL IL58493A patent/IL58493A/xx unknown
  • 1979-10-19 NO NO793379A patent/NO793379L/no unknown
  • 1979-10-22 PH PH23204A patent/PH16470A/en unknown
  • 1979-10-24 ES ES485317A patent/ES485317A1/es not_active Expired
  • 1979-10-26 AR AR278641A patent/AR219417A1/es active
  • 1979-12-07 AU AU53594/79A patent/AU531364B2/en not_active Ceased
  • 1979-12-11 MX MX798543U patent/MX7248E/es unknown
  • 1979-12-17 IE IE2440/79A patent/IE49238B1/en unknown
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  • 1979-12-18 DK DK540179A patent/DK540179A/da not_active Application Discontinuation
  • 1979-12-19 ZA ZA00796886A patent/ZA796886B/xx unknown
  • 1979-12-19 JP JP16547279A patent/JPS5584327A/ja active Pending

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